Personal care fixative

ABSTRACT

The present invention is directed to bimodal polymer compositions and personal care fixatives containing bimodal polymer compositions. The present invention includes a bimodal polymer composition having a first polymer with anionic character and a second polymer with cationic character and wherein the polymers form an interpenetrating polymer network. In one embodiment, the present invention also includes personal care fixatives (e.g., health care, hygiene or cosmetic compositions) containing the bimodal polymer composition. The present invention also includes methods for forming bimodal polymer compositions.

RELATED APPLICATION(S)

This application is a divisional of U.S. application Ser. No. 10/591,886filed on Apr. 26, 2007, which was the U.S. National Stage ofInternational Application No. PCT/2005/007925, filed Mar. 8, 2005,published as WO 2005/087191 in English, and claims the benefit under 35U.S.C. § 119 or 365 to U.S. Provisional Application No. 60/551,658,filed Mar. 9, 2004; U.S. Provisional Patent Application No. 60/606,985,filed on Sep. 3, 2004; and U.S. Provisional Patent Application No.60/627,224, filed on Nov. 12, 2004, the entire teachings of all of whichare incorporated herein by reference.

BACKGROUND OF THE INVENTION

Recent regulatory legislation and environmental concerns require thatpersonal care fixatives contain lower levels of volatile organiccompounds (VOC) than are presently found in many commercially availablefixative products. For example, desirable hair fixative compositionsshould have VOC levels of less than about 55 weight percent and shouldexhibit little or no loss in curl retention in humidity conditions, goodholding power, ease of removal and resistance to build up.

A need exists for a personal care fixative that contains lower levels ofvolatile organic compounds than the VOC levels found in currentlyavailable fixative products while retaining or improving upon thefixative properties of those currently available fixative products.

SUMMARY OF THE INVENTION

The present invention is directed to bimodal polymer compositions andpersonal care fixatives containing bimodal polymer compositions. Thepresent invention includes a bimodal polymer composition having a firstpolymer with anionic character and a second polymer with cationiccharacter and wherein the polymers form an interpenetrating polymernetwork. In one embodiment, the present invention also includes personalcare fixatives (e.g., health care, hygiene or cosmetic compositions)containing the bimodal polymer composition.

The present invention also includes methods for forming a bimodalpolymer composition. In one embodiment, a method for forming a bimodalpolymer composition includes the step of polymerizing monomers to form afirst polymer with cationic character in the presence of a secondpolymer with anionic character. In another embodiment, a method forforming a bimodal polymer composition includes the step of polymerizingmonomers to form a first polymer with anionic character in the presenceof a second polymer with cationic character.

A method for forming a bimodal polymer composition is also describedherein that includes the step of polymerizing monomers to form a firstpolymer with cationic character in the presence of a second polymer withanionic character wherein the first polymer is formed from a monomercomposition including about 35 to about 45 weight percent ammoniumderivative monomer, about 15 to about 30 weight percent water insolublemonomer, and about 5 to about 15 weight percent water soluble monomer.

Personal care fixatives containing the present bimodal polymercompositions can contain lower levels of volatile organic compounds thanthe VOC levels found in currently available fixative products. Inaddition, the present personal care fixatives can have acceptable, oreven improved, fixative properties.

Personal care fixatives containing bimodal polymer compositions of thepresent invention can gel at relatively low solids concentrations and/orat relatively high humidity conditions. Without being held to anyparticular theory, the ability of the present fixatives to gel atrelatively low solids concentrations and/or at relatively high humidityconditions is thought to be due to ionic bonding of the bimodal polymercomposition's polymer constituents. The present personal care fixativescan also gel quickly, allowing fixatives with dilute concentrations ofthe bimodal polymer composition to hold keratin-type substrates (e.g.,hair) while volatile substances contained therein, such as water oralcohol, evaporate. This quick gelling makes the bimodal polymercompositions of the present invention particularly valuable forproducing personal care fixatives that contain low VOC concentrations.In addition, ionic cross-linking is thought to produce good adhesion tokeratin-type substrates due to an increase in cohesive energy densityprovided by polar groups contained in the bimodal polymer compositions.

The bimodal polymer compositions of the present invention haveacceptable adhesion to keratin-type substances such as hair, skin,fingernails, and toenails. The bimodal compositions described herein canform polymer films with acceptable adhesion in relatively high humidityconditions from personal care fixatives having relatively lowconcentrations of volatile organic compounds. The polymer films formedfrom these inventive personal care fixatives can also provide improvedfilm properties, for example, gloss, water resistance, and abrasionresistance, in a variety of personal care applications.

The bimodal polymer compositions of the present invention represent asignificant advance over mere blends of polymers. Without being held toany particular theory, it is believed that blends of polymers containinganionic and cationic character can have only very limited stability.Further, it is believed that blends of polymers containing anionic andcationic character are limited in their ability to complex ionically.The bimodal polymer compositions of the present invention can haveincreased stability over polymer blends. In addition, it is believedthat the present bimodal polymer compositions contain ionic moieties(e.g., groups having anionic and cationic functionalities) in closeproximity to each other, whereby the polymer chains can interact in amanner generally not possible in a blend of polymers.

DETAILED DESCRIPTION OF THE INVENTION

A description of preferred embodiments of the invention follows.

The present invention is directed to bimodal polymer compositions andpersonal care fixatives containing bimodal polymer compositions. Thepresent invention includes a bimodal polymer composition having a firstpolymer with anionic character and a second polymer with cationiccharacter and wherein the polymers form an interpenetrating polymernetwork.

“Bimodal,” as that term is used herein, describes polymer compositionsthat include two polymers, one having anionic character and one havingcationic character.

An “interpenetrating polymer network,” as that term is used herein,refers to a polymer structure wherein a monomer has been polymerized inthe presence of another polymer. For example, an interpenetratingpolymer network is formed by polymerizing a monomer to form the secondpolymer in the presence of the first polymer. An interpenetratingpolymer network contains a polymer homogeneity that generally is notobtained from blending two polymers.

In one embodiment, the first polymer, the second polymer, or both thefirst and the second polymer of the bimodal polymer composition have amolecular weight of at least about 1,000 daltons, for example, rangingfrom about 1,000 to about 1,000,000 daltons, e.g., ranging from about1,000 to about 100,000 daltons or ranging from about 2,000 to about1,000,000 daltons. In one embodiment, the first polymer has a molecularweight ranging from about 1,000 to about 100,000 daltons and the secondpolymer has a molecular weight ranging from about 2,000 to about1,000,000 daltons. In another embodiment, the first polymer has amolecular weight ranging from about 2,000 to about 1,000,000 daltons andthe second polymer has a molecular weight ranging from about 1,000 toabout 100,000 daltons.

In one embodiment, the first polymer includes the carboxylate saltmonomer unit represented by Chemical Structure I:

wherein R is hydrogen or an alkyl group and X⁺ is a salt-forming cation.

An “alkyl group,” as the term is used herein, is a hydrocarbon in amolecule that is bonded to one other group in the molecule through asingle covalent bond from one of its carbon atoms. Alkyl groups can becyclic, branched or unbranched, substituted or unsubstituted, and/orsaturated or unsaturated. An alkyl group can have, for example, 1 toabout 24 carbons atoms, 1 to about 12 carbon atoms, or about 1 to about4 carbon atoms, e.g., methyl, ethyl, n-propyl, iso-propyl, n-butyl,sec-butyl and tert-butyl.

In one embodiment, the first polymer is the polymer contained in acommercially available SYNTRAN® polymer dispersion. For example, thepolymer with anionic character can be the polymer contained in, forexample, SYNTRAN® 1501, SYNTRAN® 1555, SYNTRAN® 1560, or in blendsthereof. SYNTRAN® is a trademark of Interpolymer Corporation (Canton,Mass.).

SYNTRAN® 1501, SYNTRAN® 1555, and SYNTRAN® 1560 are water-baseddispersions of polymers formed of acrylate monomers of the generalchemical formula (—CH₂—CH(COOR)—)_(n). These water-based dispersions ofpolymers generally contain about 24 to about 25 weight percent ofacrylate copolymer and about 74 to about 75 weight percent water.SYNTRAN® 1501 further contains about 1 weight percent sodiumalkylpolyethoxyethanol sulfosuccinate and about 1 weight percent sodiumlauryl sulfate. SYNTRAN® 1555 further contains about 1 weight percentsodium lauryl sulfate and about 1 weight percent sodiumlaurylpolyethoxyethanol. SYNTRAN® 1560 further contains about 1 weightpercent sodium alkylpolyethoxyethanol sulfosuccinate, about 1 weightpercent sodium lauryl sulfate, and about 1 weight percent sodiumlaurylpolyethoxyethanol.

The first polymer of the bimodal polymer composition includes, in oneembodiment, at least about 10 weight percent of carboxylate salt monomerunits. For example, the first polymer can include about 10 to about 20or about 12 to about 20 weight percent of carboxylate salt monomerunits.

In one embodiment, the second polymer includes the cationic monomer unitrepresented by Chemical Structure II:

or a quaternized adduct thereof, wherein R₁, R₃ and R₄ are,independently, hydrogen or an alkyl group and R₂ is an alkyl group.

In one embodiment, the polymer with cationic character is the polymercontained in a commercially available SYNTRAN® polymer dispersion. Forexample, the polymer with cationic character can be the polymercontained in, for example, SYNTRAN® FX30. SYNTRAN® FX30 is a water-baseddispersion of polymer that includes diethyl amino ethyl methacrylate.

In one embodiment, the second polymer (with cationic character) includesan ammonium derivative monomer unit. The ammonium derivative monomerunit can include, but is not limited to, dialkyl amino alkyl acrylates,dialkyl amino alkyl methacrylates, quaternized adducts of dialkyl aminoalkyl acrylate, quaternized adducts of dialkyl amino alkyl methacrylate,methacrylamide and esters thereof, vinyl pyrrolidone and vinylcaprolactam. In one embodiment, the ammonium derivative monomer unit isdimethylaminoethyl methacrylate or a quaternized adduct thereof. Thesecond polymer can contain about 10 to about 90 weight percent of theammonium derivative monomer unit(s). For example, the second polymer cancontain about 20 to about 80, about 30 to about 70, or about 40 to about60 weight percent ammonium derivative monomer unit(s).

In one embodiment, the second polymer includes a water insoluble monomerunit. The water insoluble monomer unit can include, but is not limitedto, esters of acrylate, esters of methacrylate, ethers of acrylate,ethers of methacrylate, styrenes, and alpha-methyl styrene. In oneembodiment, the water insoluble monomer unit is butyl methacrylate. Thesecond polymer can contain about 10 to about 90 weight percent of thewater insoluble monomer unit(s). For example, the second polymer cancontain about 20 to about 80, about 30 to about 70, or about 40 to about60 weight percent water insoluble monomer unit(s).

The second polymer can also include a water soluble monomer unit. Forexample, water soluble monomer units can include hydroxy functionalacrylates, hydroxy functional methacrylates, and alkoxylated adductsthereof such as ethoxylated and/or propoxylated adducts thereof. In oneparticular embodiment, the second polymer includes a hydroxypropylmethacrylate monomer unit. The second polymer can contain up to about 80weight percent of the water soluble monomer unit(s). For example, thesecond polymer can contain 0 to about 70, about 1 to about 50, about 5to about 25, or about 10 to about 15 weight percent water insolublemonomer unit(s).

The second polymer can include a cross-linking or multifunctionalmonomer unit. For example, the second polymer can contain amultifunctional acrylate, a multifunctional methacrylate, diallyphthalate, or any other cross-linking or multifunctional monomer unitsknown in the art. The second polymer can contain up to about 10 weightpercent of the cross-linking or multifunctional monomer unit(s). Forexample, the second polymer can contain 0 to about 10 such as about 1 toabout 5 or about 5 to about 10 weight percent cross-linking ormultifunctional monomer unit monomer unit(s).

In some embodiments, the second polymer can include a monomer unit ofanionic functionality such as, but not limited to, acrylic acid,methacrylic acid and esters thereof.

In specific embodiments, the second polymer includes an ammoniumderivative monomer unit, a water insoluble monomer unit, and optionally,a water soluble monomer unit (e.g., hydroxy functional acrylates,hydroxy functional methacrylates, and alkoxylated adducts thereof)and/or a cross-linking or multifunctional monomer unit. For example, thesecond polymer can include about 10 to about 90 weight percent of anammonium derivative monomer unit, about 10 to about 90 weight percent ofa water insoluble monomer unit, and optionally, up to about 80 weightpercent of a water soluble monomer unit (e.g., hydroxy functionalacrylates, hydroxy functional methacrylates, and alkoxylated adductsthereof) and/or up to about 10 weight percent of a cross-linking ormultifunctional monomer unit. In one particular embodiment, the secondpolymer includes about 55 to about 65 weight percent of dialkyl aminoalkyl methacrylate, about 25 to about 35 weight percent of alkylmethacrylate, and about 5 to about 15 weight percent of hydroxyfunctional methacrylate. For example, the second polymer can includeabout 55 to about 65 weight percent of dimethylaminoethyl methacrylate,about 25 to about 35 weight percent of butyl methacrylate, and about 5to about 15 weight percent of hydroxypropyl methacrylate.

In one embodiment, the first polymer is the polymer contained inSYNTRAN® 1501, SYNTRAN® 1555, SYNTRAN® 1560, or in blends thereof andthe second polymer includes an ammonium derivative monomer unit, a waterinsoluble monomer unit, and optionally, a water soluble monomer unitand/or a cross-linking or multifunctional monomer unit, as describedsupra. The first polymer (e.g., the polymer of SYNTRAN® 1501, SYNTRAN®1555, SYNTRAN® 1560, or of blends thereof) can be present in the bimodalpolymer composition in a concentration of up about 90 weight percent,for example, about 10 to about 90, about 20 to about 80, about 30 toabout 70, or about 40 to about 60 weight percent. In one embodiment, thefirst polymer can be present in the bimodal polymer composition in aconcentration of about 10 to about 30 weight percent such as about 15 toabout 25 weight percent. The second polymer can be present in thebimodal polymer composition in a concentration of up to about 90 weightpercent, for example, about 10 to about 90, about 20 to about 80, about30 to about 70, or about 40 to about 60 weight percent. In oneembodiment, the second polymer can be present in the bimodal polymercomposition in a concentration of about 1 to about 30 weight percentsuch as about 5 to about 20 weight percent.

In one embodiment, the first polymer (with anionic character) includes amonomer unit with anionic functionality. The monomer unit with anionicfunctionality can include, but is not limited to, acidic acrylatemonomer, acidic methacrylate monomer, 2-sulfoethylmethacrylate and saltsthereof, 2-acrylamido-2-methyl propanesulfonate and salts thereof,crotonic acid, itaonic acid, fumaric acid, acid anhydrides, and halfesters of di-carboxylate monomer. The first polymer can contain about 10to about 90 weight percent of monomer unit(s) with anionicfunctionality. For example, the second polymer can contain about 20 toabout 80, about 30 to about 70, or about 40 to about 60 weight percentmonomer unit(s) with anionic functionality.

In one embodiment, the first polymer includes a water insoluble monomerunit. The water insoluble monomer unit can include, but is not limitedto, esters of acrylate, esters of methacrylate, ethers of acrylate,ethers of methacrylate, styrenes, and alpha-methyl styrene. The firstpolymer can contain about 10 to about 90 weight percent of the waterinsoluble monomer unit(s). For example, the first polymer can containabout 20 to about 80, about 30 to about 70, or about 40 to about 60weight percent water insoluble monomer unit(s).

The first polymer can also include a water soluble monomer unit. Forexample, water soluble monomers can include hydroxy functionalacrylates, hydroxy functional methacrylates, and alkoxylated adductsthereof such as ethoxylated and/or propoxylated adducts thereof. Thefirst polymer can contain up to about 80 weight percent of the watersoluble monomer unit(s). For example, the first polymer can contain 0 toabout 70, about 1 to about 50, about 5 to about 25, or about 10 to about15 weight percent water insoluble monomer unit(s).

The first polymer can include a cross-linking or multifunctional monomerunit. For example, the first polymer can contain a multifunctionalacrylate, a multifunctional methacrylate, dially phthalate, or any othercross-linking or multifunctional monomer units known in the art. Thefirst polymer can contain up to about 10 weight percent of thecross-linking or multifunctional monomer unit(s). For example, the firstpolymer can contain 0 to about 10 such as about 1 to about 5 or about 5to about 10 weight percent cross-linking or multifunctional monomer unitmonomer unit(s). In one embodiment, the first polymer also includes achain modifier. Chain modifiers are known in the art and include, butare not limited to, alcohols and mercaptans.

In specific embodiments, the first polymer includes a monomer unit withanionic functionality, a water insoluble monomer unit, and optionally, awater soluble monomer unit (e.g., hydroxy functional acrylates, hydroxyfunctional methacrylates, and alkoxylated adducts thereof) and/or across-linking or multifunctional monomer unit. For example, the firstpolymer can include about 10 to about 90 weight percent of a monomerunit with anionic functionality, about 10 to about 90 weight percent ofa water insoluble monomer unit, and optionally, up to about 80 weightpercent of a water soluble monomer unit (e.g., hydroxy functionalacrylates, hydroxy functional methacrylates, and alkoxylated adductsthereof) and/or up to about 10 weight percent of a cross-linking ormultifunctional monomer unit.

In one embodiment, the first polymer includes a monomer unit withanionic functionality, a water insoluble monomer unit, and optionally, awater soluble monomer unit and/or a cross-linking or multifunctionalmonomer unit, as described supra, and the second polymer is the polymercontained in SYNTRAN® FX30. The first polymer can be present in thebimodal polymer composition in a concentration of up to about 90 weightpercent, for example, about 10 to about 90, about 20 to about 80, about30 to about 70, or about 40 to about 60 weight percent. In oneembodiment, the first polymer can be present in the bimodal polymercomposition in a concentration of about 1 to about 30 weight percentsuch as about 5 to about 20 weight percent. The second polymer (e.g.,the polymer of SYNTRAN® FX30) can be present in the bimodal polymercomposition in a concentration of up about 90 weight percent, forexample, about 10 to about 90, about 20 to about 80, about 30 to about70, or about 40 to about 60 weight percent. In one embodiment, thesecond polymer can be present in the bimodal polymer composition in aconcentration of about 10 to about 30 weight percent such as about 15 toabout 25 weight percent.

In some embodiments, substantially all or all or the carboxylate groupsof a constituent polymer of the bimodal polymer composition have beenneutralized, e.g., as salts. Neutralization can be accomplished bytechniques known in the art, for example, carboxylic acid groups of thepolymer can be reacted with one or more alkaline reagents. For example,in one embodiment, the first polymer, with anionic character, containscarboxylate groups that have been neutralized, for example, by formingcarboxylate salts.

In one embodiment, the present bimodal polymer composition includes atleast about 10 weight percent of monomer units with anionicfunctionality. For example, the bimodal polymer composition can includeat least about 20 or at least about 30 weight percent monomer units withanionic functionality. Additionally, the bimodal polymer composition caninclude at least about 10 weight percent of monomer units with cationicfunctionality. For example, the bimodal polymer composition can includeat least about 20 or at least about 30 weight percent monomer units withcationic functionality.

In one specific embodiment, the bimodal polymer composition can containless than about 40 weight percent hydroxyl-containing monomer units. Forexample, the bimodal polymer composition can contain less than about 30or less than about 20 weight percent hydroxyl-containing monomer units.

In one embodiment, the glass transition temperature (T_(g)) of thepresent bimodal polymer compositions can be indicative of the bimodalnature of the compositions. The glass transition temperature of thepresent bimodal polymer compositions can be less than about 60° C. suchas less than about 30° C.

The present invention also includes methods for forming a bimodalpolymer composition. The method can include the step of polymerizingmonomers to form a first polymer with cationic character in the presenceof a second polymer with anionic character. In one embodiment, thesecond polymer is represented by Chemical Structure I, supra. Forexample, the second polymer is represented by Chemical Structure Iwherein R is hydrogen.

In one embodiment, the bimodal polymer composition is formed by the freeradical polymerization of the first polymer monomer components in thepresence of the second polymer. For example, the bimodal polymercomposition is formed by the free radical polymerization of an ammoniumderivative monomer unit, a water insoluble monomer unit, and optionally,a water soluble monomer unit (e.g., hydroxy functional acrylates,hydroxy functional methacrylates, and alkoxylated adducts thereof)and/or a cross-linking or multifunctional monomer unit in the presenceof the second polymer (e.g., the polymer contained in SYNTRAN® 1501,SYNTRAN® 1555, SYNTRAN® 1560, and blends thereof).

In one embodiment, the second polymer is dispersed in an aqueous medium.The aqueous medium can further include, for example, salts ofalkylpolyethoxyethanol sulfosuccinate, salts of lauryl sulfate, andsalts of laurylpolyethoxyethanol. In one embodiment, the concentrationof the second polymer in the aqueous medium is about 10 to about 40weight percent such as about 20 to about 30 weight percent or about 24to about 25 weight percent. For example, water-dispersed polymers can beused such as, but not limited to, SYNTRAN® 1501, SYNTRAN® 1555, SYNTRAN®1560, and blends thereof.

The reaction of this above-described monomer composition can be moved tocomplete, or substantially complete, conversion by conventional methodsknown in the art, e.g., by emulsion polymerization, in water, solvent,or a combination thereof. The bimodal polymer composition thus obtainedcan be neutralized with an appropriate organic base or inorganic base to0 to about 100 percent of the available carboxyl groups.

In another embodiment, a method forming a bimodal polymer compositionincludes the step of polymerizing monomers to form a first polymer withanionic character in the presence of a second polymer with cationiccharacter. In one embodiment, the second polymer is represented byChemical Structure II, supra, such as diethylaminoethyl methacrylate ora quaternized adduct thereof. The bimodal polymer composition can beformed by the free radical polymerization of the first polymer monomercomponents in the presence of the second polymer. For example, thebimodal polymer composition is formed by the free radical polymerizationof a monomer unit with anionic functionality, a water insoluble monomerunit, and optionally, a water soluble monomer unit (e.g., hydroxyfunctional acrylates, hydroxy functional methacrylates, and alkoxylatedadducts thereof) and/or a cross-linking or multifunctional monomer unitin the presence of the second polymer (e.g., SYNTRAN® FX30 and thelike).

In one embodiment, the second polymer is dispersed in an aqueous medium.The aqueous medium can further include, for example, salts ofalkylpolyethoxyethanol sulfosuccinate, salts of lauryl sulfate, andsalts of laurylpolyethoxyethanol. In one embodiment, the concentrationof the second polymer in the aqueous medium is about 10 to about 40weight percent such as about 20 to about 30 weight percent or about 24to about 25 weight percent. For example, a water-dispersed polymer canbe used such as, but not limited to, SYNTRAN® FX30.

The reaction of this above-described monomer composition can be moved tocomplete, or substantially complete, conversion by conventional methodsknown in the art, e.g., by emulsion polymerization, in water, solvent,or a combination thereof. The bimodal polymer composition thus obtainedcan be neutralized with an appropriate organic acid or inorganic acid to0 to about 100 percent of the available amino groups.

General techniques associated with emulsion polymerization suitable forforming the vehicle composition of this invention are discussed in D. C.Blackley, Emulsion Polymerization (Wiley, 1975). The teachings of whichare incorporated herein by reference in their entirety. Final pH can beadjusted with a suitable cosmetically acceptable base used in thecosmetic industry. If the polymer is associated with other non-cosmeticapplications, other more aggressive bases may be incorporated.

The present invention also includes the bimodal polymer compositionsproduced by the methods described herein. In one aspect, the inventionincludes personal care fixatives that include bimodal polymercompositions produced by the methods described herein.

The bimodal polymer compositions of the present invention can be used inpersonal care products such as personal care fixatives. For example, thebimodal polymer compositions can be used in hair fixatives such as, butnot limited to, sprays, gels and mousses. In one embodiment, theinvention includes a fixative composition such as a personal carefixative. The personal care fixative can include the bimodal polymercomposition and a cosmetically acceptable medium. The cosmeticallyacceptable medium can include one or more relatively volatile solventssuch as water or an alcohol. The personal care fixative can include atotal volatile solvent concentration ranging from about 25 to about 95weight percent or more, e.g., about 30 to about 95, about 50 to about95, or about 75 to about 95 weight percent total volatile solvents. Inone embodiment, the cosmetically acceptable medium is principally waterby weight. In some embodiments, the personal care fixative is at leastabout 20, 30, 40, 50, 60, 70, 80, or at least about 90 weight percentwater. In addition, in some embodiments, the cosmetically acceptablemedium also includes an alcohol such as ethanol or panthenol.Preferably, the concentration of volatile organic compounds (VOC) suchas, for example, alcohol is less than about 55 weight percent. Forexample the VOC concentration can be less than about 50, 45, 40, 35, 30,25, 20, 15, 10, or less than 5 weight percent VOC. The personal carefixative can also contain any of the personal care fixative additivesknown to those of skill in the art. For example, the personal carefixative further can contain at least one component selected from thegroup consisting of thickening agents, dispersing agents, emulsifiers,emollients, stabilizers, surfactants, fragrances, preservatives,proteins, conditioners, colorants, dyes, plasticizers, neutralizers,glossifiers and propellants.

Application of the personal care fixatives described herein to a subject(e.g., to a human subject) typically produces a polymer film. Thepolymer film can be principally composed of the bimodal polymercomposition. In one embodiment, the polymer film is easily removed usingnormal hygiene procedures. For example, the polymer film can be watersoluble or water dispersible. In one embodiment, the polymer film isremoveable by water and soap or shampoo.

In some embodiments, the bimodal polymer compositions of the presentinvention can be used in personal care products also containing waterbased olefin, styrene and/or acrylic polymer systems such as describedin, for example, U.S. Provisional Patent Application No. 60/606,985 byWolff, et al., filed on Sep. 3, 2004, and in U.S. Provisional PatentApplication No. 60/627,224 by Wolff, et al., filed on Nov. 12, 2004, theentire teachings of both of which are incorporated herein by reference.For example, in one embodiment, the personal care product can contain anolefin graft polymer such as SYNTRAN® Olefin Graft PC 5208 (InterpolymerCorp., Canton, Mass.). In some embodiments, the personal care productcan contain an olefin graft polymer in a concentration of about 10 toabout 90 percent by polymer weight and a bimodal polymer compositionconcentration of about 90 to about 10 percent by polymer weight. Forexample, the personal care product can contain an olefin graft polymerin a concentration of about 20 to about 80 percent by polymer weight anda bimodal polymer composition concentration of about 80 to about 20percent by polymer weight.

EXEMPLIFICATION

The invention will now be further and specifically described by thefollowing examples which are not intended to be limiting.

Example 1

This example describes the production of a bimodal polymer composition.

Into a 1000 ml resin flask equipped with an agitator, condensers, andaddition ports, 500 grams SYNTRAN® 1501 (containing 25 weight percentnon-volatiles) was added. The SYNTRAN® 1501 was heated to 80° C. slowlywith a water bath and keeping the flask blanketed with an inert gas.When the temperature was reached, a premix of 40 grams of water and 0.5gram of ammonium persulfate was slowly added.

Immediately following, the following premix was added: 16 gramsdimethylaminoethyl methacrylate, 8 grams butyl methacrylate, 3 gramshydroxypropyl methacrylate, 7 grams water, and 0.5 gram C12-C15 alkylalcohol ethoxylate/10 mole. The reaction was allowed to exotherm and thetemperature was kept between about 80° C. and about 85° C. using thewater bath. The temperature was held for two hours, then 30 grams water,0.2 gram ammonium bisulfite (45% solution), and 0.5 gram aqua ammonia(28%) were added. The mixture was then held for an additional hour.

Example 2

This example describes the production of a bimodal polymer composition.

Into a 1000 ml resin flask equipped with an agitator, condensers, andaddition ports, 350 grams SYNTRAN® 1501 (containing 25 weight percentnon-volatiles) and 104 grams of water was added. The SYNTRAN® 1501 washeated to 60° C. slowly with a water bath and keeping the flaskblanketed with an inert gas. A slow, even agitation was maintained whilethe material was in the flask. When the temperature was reached, apremix of 40 grams of water and 0.5 gram of ammonium persulfate wasslowly added.

Immediately following, the following premix was added: 25 gramsdimethylaminoethyl methacrylate, 30 grams butyl acrylate, 10 gramshydroxyethyl acrylate, 15 grams water, and 1 gram C12-C15 alkyl alcoholethoxylate/10 mole. The reaction was allowed to exotherm and thetemperature was kept between about 80° C. and about 85° C. using thewater bath. The temperature was held for two hours, then 40 grams water,0.2 gram ammonium bisulfite (45% solution), and 0.5 gram aqua ammonia(28%) were added. The mixture was then held for an additional hour.

Example 3

This example describes the preparation of mousse and gel fixatives.

Preparation of Fixatives

Mousse and gel fixatives were prepared having the components listed inTables 1 and 2. (DOW CORNING® is a trademark of Dow Corning (Midland,Mich.). MACKSTAT® is a trademark of The McIntyre Group Ltd. (UniversityPark, Ill.). BRIJ® is a trademark of ICI Americas, Inc. (Wilmington,Del.).)

The bimodal polymer composition used in Mousse Fixative A and the GelFixative was produced as described in Example 1. The bimodal polymercomposition used in Mousse Fixative B was produced as described inExample 2.

TABLE 1 Gel Fixative Concen- tration (weight Weight Component Supplierpercent) (grams) Phase A Distilled Water 72.68 218 Acritimer 940 RitaCorp. 0.60 1.80 (carbomer) (Woodstock, IL) Triethanolamine PrideSolvents & Chemical 0.62 1.86 (TEA) 99% Co. (Holtsville, NY) Phase BBimodal Polymer 15 45 Composition Phase C Distilled Water 10 30 DOWCORNING ® 193 Dow Corning 0.05 0.15 Fluid (silicon fluid) (Midland, MI)Ritapan DL (panthenol) Rita Corp. 0.10 0.30 (Woodstock, IL) Promois WG(hydrolyzed Rita Corp. 0.05 0.15 wheat protein) (Woodstock, IL) PromoisWG-SIG Rita Corp. 0.05 0.15 (hydrolyzed wheat (Woodstock, IL) proteinPG-Propyl Methylsilanediol) MACKSTAT ® DM-LO The McInryre Group Ltd.0.40 1.20 (DMDM Hydantoin) (University Park, IL) Phase D BRIJ ® 98 VegUniqema 0.35 1.05 (Oleth-20) (New Castle, DE) Fragrance #98444 Intarome(Norwood, NJ) 0.1 0.30 Total: 100 300

The Gel Fixative, having a composition as shown in Table 1, was preparedby mixing Phase A components. Separately, Phase C and D were mixed.Phases C and D were then warmed and then Phase D was added to Phase C.Phases C and D were then stirred until the mixture was homogeneous. Themixture of Phases C and D were then added to Phase A and stirred.Finally, Phase B was added to the mixture of Phases A, C and D and theresulting mixture was stirred until homogeneous.

TABLE 2 Mousse Fixatives A and B Concen- tration (weight WeightComponent Supplier percent) (grams) Phase A Distilled Water 87.95 263.85Ritapan DL (panthenol) Rita Corp. 0.50 1.50 (Woodstock, IL) DOWCORNING ® 193 Dow Corning 0.50 1.50 Fluid (silicon fluid) (Midland, MI)Bimodal Polymer 10 30 Composition MACKSTAT ®DM-LO The McIntyre GroupLtd. 0.40 1.20 (DMDM Hydantoin) (University Park, IL) Promois WG(hydrolyzed Rita Corp. 0.10 0.30 wheat protein) (Woodstock, IL) PromoisWG-SIG Rita Corp. 0.10 0.30 (hydrolyzed wheat (Woodstock, IL) proteinPG-Propyl Methylsilanediol) Phase B PEG-40 Hydrogenated Lipo Chemicals,Inc. 0.05 0.15 Castor Oil (Paterson, NJ) Fragrance # 98444 Intarome(Norwood, NJ) 0.10 0.30 Polysorbate 20 (PEG-10 Lipo Chemicals, Inc. 0.300.90 Sorbitan Laurate) (Paterson, NJ) Total: 100 300

Mousse Fixatives A and B, having compositions as shown in Table 2, wereprepared by adding together Phase A components in the listed orderfollowed by stirring until Phase A was homogeneous. Phase B was thenprepared by mixing the listed components. Phase B was added to Phase Aand the mixture was stirred until homogeneous.

Evaluation of Fixative Compositions

Several 24 cm tresses of European Brown hair (from same lot of hair)were prepared. Each tress weighed about 6.5 grams. Each tress was washedthoroughly with a strong detergent to remove any residual materials andexcess water was removed.

Mousse Application

About 0.5 grams of mousse fixative was applied to each of a set oftresses and was gently spread through the hair. The tips of the hairwere then rolled about a ¾ inch to 1 inch curling rod. The tresses wereclamped to the curling rods and dried for about five days in air at roomtemperature.

Gel Application

About 0.8 grams of the gel fixative was applied to each of a set oftresses and was gently spread through the tresses. Each tress was thencombed through tress once with fine end of a comb to distribute the gelfixative composition. The tips of the hair were then rolled about a ¾inch to 1 inch curling rod. The tresses were clamped to the curling rodsand dried for about 5 days in air at room temperature.

The dry hair was removed from the curling rods and hung on calibratedboards. The length of the curl was measured. The curled hair was placedin a humidity chamber and position of bottom of curl was noted atprescribed time intervals. The humidity chamber had an averagetemperature of 82.7° F. and an average humidity of 96.7 percent relativehumidity. Table 3 shows the percent curl retention for the Gel Fixative,Mousse Fixatives A and B, and 3 comparative fixatives (CARBOPOL® PolymerGel, PVP K90 Mousse, and PVP K30 Mousse). The comparative fixatives wereprepared by substituting a CARBOPOL® polymer, polyvinyl pyrrolidone(PVP) K90 and PVP K30, respectively, for the bimodal polymer compositionin the gel and mousse formulations of Tables 1 and 2. CARBOPOL® is atrademark of Noveon IP Holdings Corp. (Cleveland, Ohio). The PVP K90 andPVP K30 were obtained from ISP Technologies, Inc. (Wayne, N.J.).

TABLE 3 Hair Curl Retention Using Various Fixatives Gel PVP Mouse PVPMouse Fixa- CARBOPOL ® K90 Fixative K30 Fixative tive Polymer Gel MousseA Mousse B Initial 4.4 4.5 4.0 4.0 3.7 4.5 Curl Length (cm) Final 6.515.3 12.1 4.7 16.0 6.5 Curl Length (cm) Time (hours) Curl RetentionPercentage: 1 96.9 97.4 96.0 100 81.3 92.8 2 94.4 66.7 96.5 100 64 92.33 89.8 48.7 73.5 96.5 46.8 89.7 4 89.8 44.6 65 96.5 41.9 89.7 5 89.344.6 59.5 96.5 39.4 89.7

Example 4

This example describes three hair fixative compositions.

Pump Composition A—(Crisp Character) (5% Non-Volatiles)

bimodal polymer composition 20 grams (g) water 24.6 g amino methylpropanol (AMP) 0.4 g ethyl alcohol, denatured (SDA-40) 55 g

The water, SDA-40 and AMP are mixed and the bimodal polymer compositionis slowly added with good agitation until dispersed.

Pump Composition B—(Flexible Hold) (5% Non-Volatiles)

bimodal polymer composition 20 grams (g) water 23.3 g amino methylpropanol (AMP) 0.5 g Crovol PK-70 (Croda, Inc., Parsippany, NJ) 0.4 gDOW CORNING ® 190 Fluid 0.4 g (Dow Corning Midland, MI) 1,3-butyleneglycol 0.4 g ethyl alcohol, denatured (SDA-40) 55.0 g

All ingredients except for the bimodal polymer composition are mixedwith good agitation. The bimodal polymer composition is then added tothe mixture with continued agitation.

Pump Composition C—(Low Static) (5% Non-Volatiles)

bimodal polymer composition 14.4 grams (g) water 21.9 g amino methylpropanol (AMP) 0.5 g Crovol PK-70 (Croda, Inc., Parsippany, NJ) 0.8 gDOW CORNING ® 190 Fluid 1.2 g (Dow Corning Midland, MI) panthenol 0.8 gethyl alcohol, denatured (SDA-40) 55 g Statran 1705 (Interpolymer Corp,Canton, MA) 1.2 g

All of the ingredients are mixed with good agitation except the bimodalpolymer composition and Statran 1705. The Statran 1705 is slowly addedand allowed to mix. After the Statran 1705 is dispersed, the bimodalpolymer composition is slowly added and agitated until dispersed.

Example 5

This example describes the production of a bimodal polymer composition.

Into a 1000 ml resin flask equipped with an agitator, condensers, andaddition ports, the following was added:

Water 293 grams (g) Sodium lauryl sulfate (30%) 2.4 g SodiumAlkylpolyethoxyethanol sulfosuccinate 1.8 gThis was heated via water bath and under inert gas to 80 C. With goodagitation the following was added over a one hour period:

Butyl Acrylate 11.6 g Ethyl Acrylate 46.7 g Methyl Methacryalte 29.2 gMethacrylic Acid 22.1 g Styrene 7.0 gAfter the mixture had agitated for 15 minutes, a premix of 0.5 grams ofammonium persulfate in 40 grams of water was added followed by 0.2 gramsof ammonium bisulfite solution (45%). The reaction was allowed toproceed and the temperature was maintained below 80 C. The mixture washeld for two hours at the peak temperature. The following was added atthis time:

Water 26 g Aqua Ammonia 28% 13 gThis was mixed until it became uniform in appearance.A second mixture of ammonium persulfate, 0.5 grams in 40 grams of waterwas added and immediately followed with:

Dimethylaminoethyl methacrylate 15.5 g Ethyl Acrylate 7.8 g MethylMethacrylate 15.5 gThe mixture was allowed to exotherm and was held between 80 and 85 C fortwo hours. The mixture was then cooled and filtered.

Example 6

This example describes the preparation of a Texturizing Shampoo.

A Texturizing Shampoo was prepared having the components listed in Table4. DISSOLVINE—is a trademark of Akzo Nobel (Chicago, Ill.), RITAPAN is atrademark of RITA Corp. (Woodstock, Ill.), MACKADET—is a trademark ofThe McIntyre Group Ltd. (University Park, Ill.), GERMALL—is a trademarkof the ISP Corp. (Wayne, N.J.).

TABLE 4 Texturizing Shampoo Concen- tration (weight Weight ComponentSupplier percent) (grams) Phase A Distilled Water 42.93 128.79DISSOLVINE-Na₂S Akzo Nobel (Chicago, IL) 0.10 0.30 Ritapan DL Rita Corp.0.50 1.50 (Woodstock, IL) Phase B SYNTRAN- Olefin Interpolymer Corp.8.00 24.00 Graft PC 5208 (Canton, MA) SYNTRAN- Bimodal InterpolymerCorp. 2.00 6.00 PC 5100 (Canton, MA) Phase C MACKADET- APB The McIntyreGroup Ltd. 45.00 135.00 (University Park, IL) Phase D GERMALL- Plus ISPCorp. (Wayne, NJ) 0.35 1.05 Fragrance Carrubba Inc. 0.30 0.90 (Milford,CT) Citric Acid 0.02 0.06 Sodium Chloride 0.80 2.40 Sodium Chloride 0.30(viscosity adjustment) Total: 100 300

The Texturizing Shampoo, having a composition as shown in Table 4, wasprepared by heating water to 45° C. to 50° C. and mixing Phase Acomponents. Separately Phase B was added at 45° C. to Phase A. Then,Phase C was added at 45° C. Finally, Phase D was added to the mixture ofPhases A, B and C at 35° C. and the resulting mixture was stirred untilhomogenous.

Example 7

This example describes the preparation of a 35% VOC Hair Spray.

The 35% VOC Hair Spray was prepared having the components listed inTable 5. AMP-95—is a trademark of Angus Corp. (Chicago, Ill.), DOWCORNING is a trademark of Dow Corning (Midland, Mich.), CROVOL is atrademark of Croda Inc. (Parsippany, N.J.).

TABLE 5 Low VOC Hair Spray Concen- tration (weight Weight ComponentSupplier percent) (grams) Phase A SDA-40B 200 70.00 210.00 Proof AMP-95-Angus Corp. (Chicago, IL) 0.50 1.50 DC 193 Fluid Dow Corning (Midland,MI) 0.10 0.30 Crovol PK-70 Croda Inc. 0.05 0.15 (Parsippany, NJ) Phase BSYNTRAN-KL- Interpolymer Corp. 10.00 30.00 219C (Canton, MA) SYNTRAN-Interpolymer Corp. 19.35 58.05 EX 107-21-3 (Canton, MA) AMP-95- AngusCorp. (Chicago, IL) Sufficient quantity to adjust pH to 8.5-8.7 Total(100% Concentration): 100 300 Hair Spray Formulation: 35% VOCConcentrate 50% Propellant 50%

The 35% VOC Hair Spray, having a composition as shown in Table 5, wasprepared by mixing Phase A components and stirring between eachcomponent until homogenous. Phase B ingredients were separately added aslisted, stirring between each ingredient until homogenous. Phase B wasadded to Phase A and the mixture was stirred until homogenous.

The low VOC hair spray had the following average particle size:

Valve specification: 020 MB Conclave Kosmos, o18 S90 Stem, 025×013 VTS90Average Particle Size: 30.18 microns

While this invention has been particularly shown and described withreferences to preferred embodiments thereof, it will be understood bythose skilled in the art that various changes in form and details may bemade therein without departing from the scope of the inventionencompassed by the appended claims.

1. A method for forming a bimodal polymer composition, comprising thestep of polymerizing monomers to form a first polymer with cationiccharacter in the presence of a second polymer with anionic character. 2.The method of claim 1 wherein the second polymer includes the followingcarboxylate salt monomer unit:

wherein R is hydrogen or an alkyl group and X⁺ is a salt-forming cation.3. The method of claim 2 wherein the second polymer is dispersed in anaqueous medium.
 4. The method of claim 3 wherein the aqueous mediumincludes at least one compound selected from the group consisting of:salts of alkylpolyethoxyethanol sulfosuccinate, salts of lauryl sulfateand salts of laurylpolyethoxyethanol.
 5. The method of claim 1 whereinemulsion polymerization is used to polymerize monomers to form the firstpolymer in the presence of the second polymer.
 6. A method for forming abimodal polymer composition, comprising the step of polymerizingmonomers to form a first polymer with anionic character in the presenceof a second polymer with cationic character.
 7. The method of claim 6wherein the second polymer includes the following cationic monomer unit:

or a quaternized adduct thereof, wherein R₁, R₃ and R₄ are,independently, hydrogen or an alkyl group and R₂ is an alkyl group. 8.The method of claim 7 wherein the cationic monomer unit includes diethylamino ethyl methacrylate or a quaternized adduct thereof.
 9. The methodof claim 6 wherein emulsion polymerization is used to polymerizemonomers to form the first polymer in the presence of the secondpolymer.
 10. A method for forming a bimodal polymer composition,comprising the step of polymerizing monomers to form a first polymerwith cationic character in the presence of a second polymer with anioniccharacter wherein the first polymer is formed from a monomer compositionincluding about 35 to about 45 weight percent ammonium derivativemonomer, about 15 to about 30 weight percent water insoluble monomer,and about 5 to about 15 weight percent water soluble monomer.
 11. Themethod of claim 10 wherein the second polymer includes the followingcarboxylate salt monomer unit:

wherein R is hydrogen or an alkyl group and X⁺ is a salt-forming cation.12. The method of claim 11 wherein the second polymer is dispersed in anaqueous medium.
 13. The method of claim 10 wherein the weight ratio ofthe first polymer to the second polymer is about 0.1 to about 2.